CN103474663B - Lithium ion battery, positive electrode and preparation method thereof - Google Patents
Lithium ion battery, positive electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof, additionally provides the lithium ion battery using above-mentioned positive electrode.Anode material for lithium-ion batteries has the melting structure that stratiform stratiform spinel symbiotic is formed, and internal layer is stratiform cobalt acid lithium, and intermediate layer is stratiform nickel ion doped, and outermost layer is spinel nickel LiMn2O4；It is used in presoma Co3O4Surface coating NiMn oxides, then the mode with lithium salts mixed sintering be made.Compared with prior art, the anode material for lithium-ion batteries of symbiotic structure of the present invention has higher discharge capacity and excellent cycle performance under high voltages.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of lithium-ion electric of symbiotic structure
Pond positive electrode and preparation method thereof, and the lithium ion battery using above-mentioned material.
Background technology
Lithium ion battery generally comprises positive plate, negative plate, the barrier film being interval between positive/negative plate, and electrolysis
Liquid, wherein, positive plate includes plus plate current-collecting body and the positive electrode being distributed on plus plate current-collecting body, and negative plate includes negative pole currect collecting
Body and the negative material being distributed on negative current collector.Currently used lithium ion anode material is LiCoO2、LiNi1/3Co1/ 3Mn1/3O2、LiMn2O4、LiFePO4Deng, but the defects of these positive electrodes have itself, such as：LiCoO2Overcharge resistance performance it is poor,
Gram volume plays limited under 4.2V；LiNi1/3Co1/3Mn1/3O2Exist compacted density it is low, with the poor compatibility of electrolyte, Soft Roll
The problems such as flatulence；LiMn2O4Circulation and storage performance then at high temperature is all bad；LiFePO4Exist cryogenic property it is bad, production
The problems such as product uniformity difference.
With the increasingly lightening development of the consumption electronic products such as mobile phone, flat board, the positive electrode of pursuit higher energy density
The focus of lithium ion battery development is turned into.Due to volume energy density=discharge capacity * discharge voltage plateaus * compactings of battery
Density, therefore it is exactly the charge cutoff voltage for improving battery to improve one of effective means of energy density, improves discharge capacity, enters
And improve the volume energy density of battery.
Inventor, which studies, to be found：With LiCoO2(i.e. positive active material is exemplified by 2430 button cells of/Li systems
LiCoO2, negative electrode active material is lithium piece), when charge cutoff voltage is 4.2V, LiCoO2Electric discharge gram volume be about 144mAh/
g；When operating voltage is improved to 4.3V, LiCoO2Electric discharge gram volume be about 160mAh/g；When operating voltage is improved to 4.4V,
LiCoO2Electric discharge gram volume be about 175mAh/g；When operating voltage is improved to 4.5V, LiCoO2Electric discharge gram volume be about
190mAh/g；And operating voltage further improve to 4.6V when, LiCoO2Electric discharge gram volume about reach 220mAh/g.But
After blanking voltage improves, when particularly bringing up to more than 4.4V, LiCoO2Structure become unstable, the cyclicity under high voltage
It can be deteriorated, while also bring a series of safety problems such as heat endurance difference under high voltage.It can be seen that in order to by improving charge cutoff
Voltage improves the discharge capacity of battery and energy density, first will solve to bring all because charge cutoff voltage is improved
More problems.
At present, it is generally considered that cladding can improve the surface texture stability of positive electrode, improves it under high voltages
Cycle performance, therefore lot of domestic and international document and patent give and much utilize Al2O3、AlPO4、ZrO2、TiO2、B2O3Deng oxygen
The positive electrode of compound cladding.But found in practical operation, the effect of metal oxide cladding is very limited, and because metal
Oxide is non-electroactive materials, therefore very poor to the conductibility of lithium ion, can sacrifice positive electrode after cladding on the contrary
Gram volume and discharge voltage plateau, the energy density of positive electrode is also just sacrificed to a certain extent, it is negative equivalent to bringing
Face effect.
Therefore, it has been proposed that using coprecipitation in Co3O4Surface coating layer of NixMny(OH)z, obtain presoma gradient
Material [NixMny(OH)z]n·(Co3O4)1-nAfterwards, tempering sinters at a certain temperature, forms the oxide of gradient-structure
[NixMnyOz]n·(Co3O4)1-n；Then plus lithium carries out double sintering, you can obtains with the high-tension gradient positive pole of high-pressure solid
Material.
But the above method still suffers from following shortcoming：1) it is readily incorporated foreign ion：From nickel sulfate, manganese sulfate conduct
Nickel source, manganese source are co-precipitated, and can inevitably introduce foreign ion SO4 2-, so that having a negative impact to battery；2)
NiMn ratios are uneven：Mn(OH)2MnO (OH) is easily oxidized under high ph-values in coprecipitation process2And formed " partially
Analysis ", therefore the NiMn stoichiometric proportions in formed positive electrode are difficult to reach expected.
In view of this, it is necessory to provide a kind of positive electrode constitutionally stable under high voltages and preparation method thereof, with
Improve the energy density of lithium ion battery.
The content of the invention
It is an object of the invention to：A kind of Stability Analysis of Structures under high voltages is provided and does not influence lithium ion battery other performance
Positive electrode, to ensure that there is higher discharge capacity and energy density using the lithium ion battery of the positive electrode, simultaneously
With more excellent cycle performance.
In order to realize foregoing invention purpose, present inventor has found by further investigation：Cobalt acid lithium is followed in high voltage
Structural stability difference is because it is in 4.53V (vs Li during ring+/ Li) nearby in the presence of the phase transformation by the opposite H1-3 phases of O3, should
Transition process invertibity is poor, causes Co-O bond energys to die down, and Co dissolutions are more and capacity attenuation is accelerated；In view of stratiform
LiNi0.5Mn0.5O2With spinelle LiNi0.5Mn1.5O4Structural stability be all better than LiCoO2, therefore the positive pole material of symbiotic structure
Material should have more preferable stability, it is possible to increase the Co-O bond energys of cobalt acid lithium, effectively suppress cobalt acid during high voltage cycle
The structure collapses of lithium, suppress Co dissolutions, so as to improve the invertibity of high voltage removal lithium embedded.In terms of interlayer arrangement, due to
LiNi0.5Mn0.5O2It can reach more than 180mAh/g in 3.0~4.5V reversible capacity, there is higher discharge capacity, and
Easily merged between stratiform and stratiform, symbiosis, thus LiNi may be selected0.5Mn0.5O2As intermediate layer, with inside
LiCoO2Symbiosis；The LiNi of spinel structure0.5Mn1.5O4With 4.7V charging/discharging voltage platforms, gram volume is played in 130mAh/g
More than, thus be suitable as outermost layer and carry out symbiosis.In addition, XRD researchs are, it was also found that during high voltage cycle, cobalt acid lithium C
Axle expansion is larger, and symbiotic structure can suppress the expansion of its C axle under high voltages, be followed so as to improve the high voltage of positive electrode
Ring invertibity.
Accordingly, the invention provides a kind of anode material for lithium-ion batteries, it has stratiform-layered-spinel symbiosis shape
Into melting structure, internal layer is stratiform cobalt acid lithium, and intermediate layer is stratiform nickel ion doped, and outermost layer is spinel nickel LiMn2O4；Institute
The biomolecule expressions for stating positive electrode are：
(1-x-y)LiCoO2·x(LiNi0.5-aMn0.5-bWa+bO2)·y(LiNi0.5-cMn1.5-dVc+dO4),
Wherein, at least one of W Al, Mg, Ti, Sr, La element, at least one of V Al, Mg, Ti, Sr, La
Element, W, V element may be the same or different, the ＜ ＜ c of a, b≤0.2,0 of 0 ＜ x ＜, 0.1,0 ＜ y ＜ 0.1,0, d≤0.2.
So-called symbiosis, refers to centered on cobalt acid lithium, and it is wrapped with stratiform nickel ion doped, and outermost layer is enclosed with spinelle
Nickel ion doped, this positive electrode have two kinds of structures of stratiform and spinelle；Two kinds of structures are once formed in building-up process,
And certain synergy can occur and play both advantages：That is the capacity of layer structure cobalt acid lithium is high, stratiform nickel ion doped
Capacity it is high and structural stability is preferable, the stability of spinel nickel LiMn2O4 is good and high voltage cycle is good, above-mentioned symbiosis knot
Structure causes this positive electrode to have good structural stability and cycle life under high voltages.If on the contrary, stratiform nickel manganese
The structure of sour lithium and spinel nickel LiMn2O4 is mutually replaced in position, then the stratiform nickel ion doped of high power capacity can be anti-in electrochemistry
Gradually come off and lose the effect for improving capacity during answering.
One kind as anode material for lithium-ion batteries of the present invention is improved, its median particle diameter D50For 6~25 μm.Reason exists
In：Median particle diameter is too small, can reduce the compacted density of made positive plate；Particle diameter is excessive, chemical property can be caused to be deteriorated again.
One kind as anode material for lithium-ion batteries of the present invention is improved, during the melt surface of its melting structure is short grained
It is worth particle diameter D50For 0.01~5 μm, preferably 0.01~2 μm.Reason is：Melting little particle particle diameter is excessive, and it is in cold pressure procedure
In be easily broken, influence chemical property, cause capacity attenuation fast.
One kind as anode material for lithium-ion batteries of the present invention is improved, and the characteristic infrared absorption peak value of wherein Co-O keys is
570~576cm-1。
One kind as anode material for lithium-ion batteries of the present invention is improved, and it charges to 4.5V (vs Li+/ Li) under XRD
003 corresponding peak does not divide.
One kind as anode material for lithium-ion batteries of the present invention is improved, and its BET is 0.1~0.9m2/g.Reason is：
The too small chemical properties that can influence battery of BET, BET is excessive and can make it that the side reaction of positive pole and electrolyte is excessive, cyclicity
It can be deteriorated.
One kind as anode material for lithium-ion batteries of the present invention is improved, and its expression formula is：
0.96LiCoO2·0.02LiNi0.4Mn0.4Mg0.2O2·0.02LiNi0.45Mn1.45Al0.1O4、
0.90LiCoO2·0.09LiNi0.45Mn0.45La0.1O2·0.01LiNi0.48Mn1.4Mg0.12O4、
0.90LiCoO2·0.01LiNi0.45Mn0.45Al0.05Sr0.05O2·0.09LiNi0.4Mn1.4Ti0.2O4、
0.91LiCoO2·0.04LiNi0.47Mn0.48La0.05O2·0.05LiNi0.42Mn1.48La0.1O4Or
0.90LiCoO2·0.03LiNi0.5Mn0.48Ti0.02O2·0.07LiNi0.45Mn1.45Sr0.1O4。
Relative to prior art, anode material for lithium-ion batteries of the present invention has what stratiform-layered-spinel symbiosis was formed
Melting structure, wherein internal layer are stratiform cobalt acid lithium, and intermediate layer is stratiform nickel ion doped, and outermost layer is spinel nickel LiMn2O4, this
Kind of symbiotic structure has a higher discharge capacity and excellent cycle performance under high voltages, the stratiform nickel ion doped in intermediate layer and most
The spinel nickel LiMn2O4 of outer layer effectively protects the structural stability of internal stratiform cobalt acid lithium, effectively restrains cobalt acid lithium in height
Co dissolutions during voltage cycle, the invertibity of positive electrode removal lithium embedded under high voltage is improved, and from high voltage
Under can also play available capacity, therefore further improve the energy density of positive electrode.In addition, more hold between stratiform and stratiform
Symbiosis easily occurs, so selection stratiform nickel ion doped, as intermediate layer, the more stable spinel nickel LiMn2O4 of structure is as outermost
Layer.
In order to realize foregoing invention purpose, the present invention also provides one kind and is preparing lithium ion battery described in any of the above-described paragraph just
The method of pole material, it comprises the following steps：
1) according to chemical dosage ratio Ni：Mn：W=(0.5-a)：(0.5-b)：(a+b), by soluble nickel salt, manganese salt and other
Inorganic salts are dissolved in the first solvent, form the first mixed solution；First chelating agent is dissolved in the second solvent, and by the first chela
Mixture solution, which is added in the first mixed solution, obtains the second mixed solution；The second mixed solution pH is adjusted as 4~8；
2) by Co3O4It is added in the second mixed solution, is evaporated after being stirred, is calcined at a certain temperature, obtain by nickel
The Co of manganese cladding3O4, i.e. (1-x) Co3O4·x(Ni0.5-aMn0.5-bWa+bO2)；
3) according to chemical dosage ratio Ni：Mn：V=(0.5-c)：(1.5-d)：(c+d), by soluble nickel salt, manganese salt and other
Inorganic salts are dissolved in the 3rd solvent, form the 3rd mixed solution；Second chelating agent is dissolved in the 4th solvent, and by the second chela
Mixture solution is added in the 3rd mixed solution and obtains the 4th mixed solution；The pH for adjusting the 4th mixed solution is 4~8；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.5-aMn0.5-bWa+bO2) it is added to the 4th mixing of step 3)
In solution, it is evaporated after being stirred, is calcined at a certain temperature, obtain：
(1-x-y)Co3O4·x(Ni0.5-aMn0.5-bWa+bO2)·y(Ni0.5-cMn1.5-dVc+dO4)；
5) product for obtaining step 4) is mixed with lithium salts, is calcined, and obtains the lithium of stratiform-layered-spinel symbiotic structure
Ion battery positive electrode.
One kind as method for preparing anode material of lithium-ion battery of the present invention is improved, in the step 1) and step 3),
Soluble nickel salt is nickel acetate and/or nickel nitrate；Soluble manganese salt is manganese acetate and/or manganese nitrate；Other inorganic salts are solvable
At least one of aluminium salt, magnesium salts, titanium salt, lanthanum salt and strontium salt of property；First to fourth solvent may be the same or different, and be taken respectively from
At least one of water, ethanol and isopropanol；The one the second chelating agents may be the same or different, and be taken respectively from citric acid, tartaric acid
With at least one of gluconic acid.
One kind as method for preparing anode material of lithium-ion battery of the present invention is improved, in the step 2) and step 4),
Sintering temperature is 400~1000 DEG C, and roasting time is 1~20h, and calcination atmosphere is air or oxygen.Because considering Mn in oxygen
Middle calcining can generate less Mn3+, thus preferably oxygen atmosphere is calcined to material.
One kind as method for preparing anode material of lithium-ion battery of the present invention is improved, and in the step 5), lithium salts is
Li2CO3, LiOH and LiNO3At least one of, sintering temperature is 800~1050 DEG C, and roasting time is 1~20h, calcination atmosphere
For air or oxygen.
Compared with prior art, preparation method of the present invention is used in presoma Co3O4Surface coating NiMn oxides, then
With the mode of lithium salts mixed sintering, the anode material for lithium-ion batteries of stratiform-layered-spinel symbiotic structure is formed, makes use
The lithium ion battery of this positive electrode discharge capacity under high voltages, cycle performance are all significantly improved.In addition, this hair
Bright preparation method also has the advantages of technique is simple, does not introduce foreign ion, will not occur " to be segregated ", therefore is easily achieved production
Industry metaplasia is produced.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium ion battery, and it includes positive plate, negative pole
Piece, the barrier film being placed between positive/negative plate, and electrolyte, positive plate include plus plate current-collecting body and are arranged at plus plate current-collecting body
On positive electrode active material layer, positive electrode active material layer using the symbiotic structure described in any of the above-described paragraph lithium ion battery just
Pole material is as positive active material.
One kind as lithium ion battery of the present invention is improved, and it is 4.3V~4.7V relative to the charge cutoff voltage of lithium.
Relative to prior art, lithium ion battery of the present invention has used the positive electrode of above-mentioned symbiotic structure, thus in height
Have very high discharge capacity and excellent cycle performance under voltage, and the raising of charge cutoff voltage then cause the battery have compared with
High volume energy density, so disclosure satisfy that the demand that people are thinned to lithium ion battery.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments to anode material for lithium-ion batteries of the present invention, preparation method and lithium ion
The technique effect of battery is further elaborated, in accompanying drawing：
Fig. 1 is SEM (SEM) figure of the positive electrode of the embodiment of the present invention 1.
Fig. 2 is that the SEM of the positive electrode of comparative example 1 schemes.
Fig. 3 is infrared (FTIR) spectrogram of positive electrode of the embodiment of the present invention 1 and comparative example 1, wherein, A is embodiment 1, B
For comparative example 1.
Fig. 4 is the XRD spectra of the positive electrode of the embodiment of the present invention 1 and comparative example 1, wherein, A be embodiment 1, B for than
Compared with example 1.
Fig. 5 be the positive electrode of the embodiment of the present invention 1 and comparative example 1 in the range of 3.0-4.6V, 0.5C/0.5C discharge and recharges
The specific discharge capacity of circulation-circulation comparison diagram, wherein, A is embodiment 1, and B is comparative example 1.
Embodiment
In order that goal of the invention, technical scheme and the advantageous effects of the present invention become apparent from, with reference to embodiments
The present invention is described in further detail with accompanying drawing, it is to be understood that embodiments of the invention are merely to explain this hair
It is bright, the limitation present invention is not intended to, and embodiments of the invention are not limited to the embodiment that is provided in specification.
Embodiment 1
The present embodiment is 0.96LiCoO2·0.02LiNi0.4Mn0.4Mg0.2O2·0.02LiNi0.45Mn1.45Al0.1O4Symbiosis
The anode material for lithium-ion batteries of structure, the BET of the positive electrode is 0.26m2/ g, D50=15 μm, the short grained D of melt surface50
=1μm。
The preparation process of above-mentioned positive electrode is：
1) according to chemical dosage ratio Ni：Mn：Mg=0.4：0.4：0.2, by the nickel acetate, manganese acetate and nitric acid of certain mass
Magnesium is dissolved in the water, and forms the first mixed solution；Citric acid is soluble in water, and it is molten that citric acid solution is added into the first mixing
The second mixed solution is obtained in liquid；The second mixed solution pH is adjusted as 8；
2) by the Co of certain mass3O4It is added in the second mixed solution, is evaporated after being stirred, under 700 degree of air atmosphere
10h is calcined, obtains (1-x) Co3O4·x(Ni0.4Mn0.4Mg0.2O2)；
3) according to chemical dosage ratio Ni：Mn：Al=0.45：1.45：0.1, by the nickel nitrate, manganese nitrate and nitre of certain mass
Sour aluminium is dissolved in ethanol, forms the 3rd mixed solution；Tartaric acid is dissolved in ethanol, and tartaric acid solution is added to the 3rd
The 4th mixed solution is obtained in mixed solution；The pH for adjusting the 4th mixed solution is 5；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.4Mn0.4Mg0.2O2) be added to step 3) the 4th mixing it is molten
In liquid, it is evaporated after being stirred, 10h is calcined at 800 DEG C of oxygen atmosphere, obtains (1-x-y) Co3O4·x
(Ni0.4Mn0.4Mg0.2O2)·y(Ni0.45Mn1.45Al0.1O4)；
5) product that step 4) obtains is mixed with lithium salts, 10h is calcined at 950 DEG C of oxygen atmosphere, obtain the positive pole of embodiment 1
Material 0.96LiCoO2·0.02LiNi0.4Mn0.4Mg0.2O2·0.02LiNi0.45Mn1.45Al0.1O4。
Embodiment 2
The present embodiment is 0.90LiCoO2·0.09LiNi0.45Mn0.45La0.1O2·0.01LiNi0.48Mn1.4Mg0.12O4Altogether
The anode material for lithium-ion batteries of raw structure, the BET of the positive electrode is 0.18m2/ g, D50=22 μm, melt surface is short grained
D50=0.02μm。
The preparation process of above-mentioned positive electrode is：
1) according to chemical dosage ratio Ni：Mn：La=0.45：0.45：0.1, by the nickel nitrate, manganese acetate and nitre of certain mass
Sour lanthanum is dissolved in isopropanol, forms the first mixed solution；Gluconic acid is soluble in water, and gluconic acid solution is added to
The second mixed solution is obtained in first mixed solution；The second mixed solution pH is adjusted as 6；
2) by the Co of certain mass3O4It is added in the second mixed solution, is evaporated after being stirred, under 400 degree of air atmosphere
2h is calcined, obtains (1-x) Co3O4·x(Ni0.45Mn0.45La0.1O2)；
3) according to chemical dosage ratio Ni：Mn：Mg=0.48：1.4：0.12, by the nickel nitrate, manganese nitrate and nitre of certain mass
Sour magnesium is dissolved in ethanol, forms the 3rd mixed solution；Tartaric acid is dissolved in ethanol, and tartaric acid solution is added to the 3rd
The 4th mixed solution is obtained in mixed solution；The pH for adjusting the 4th mixed solution is 8；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.45Mn0.45La0.1O2) be added to step 3) the 4th mixing it is molten
In liquid, it is evaporated after being stirred, 3h is calcined at 1000 DEG C of oxygen atmosphere, obtains (1-x-y) Co3O4·x
(Ni0.45Mn0.45La0.1O2)·y(Ni0.48Mn1.4Mg0.12O4)；
5) product that step 4) obtains is mixed with lithium salts, 20h is calcined at 850 DEG C of air atmosphere, obtain the positive pole of embodiment 2
Material 0.90LiCoO2·0.09LiNi0.45Mn0.45La0.1O2·0.01LiNi0.48Mn1.4Mg0.12O4。
Embodiment 3
The present embodiment is 0.9LiCoO2·0.01LiNi0.45Mn0.45Al0.05Sr0.05O2·0.09LiNi0.4Mn1.4Ti0.2O4
The anode material for lithium-ion batteries of symbiotic structure, the BET of the positive electrode is 0.60m2/ g, D50=7 μm, melt surface little particle
D50=0.1μm。
The preparation process of above-mentioned positive electrode is：
1) according to chemical dosage ratio Ni：Mn：Al：Sr=0.45：0.45：0.05：0.05, by the nickel nitrate of certain mass, nitre
Sour manganese, aluminium isopropoxide and strontium nitrate are dissolved in isopropanol, form the first mixed solution；Citric acid is soluble in water, and by lemon
Lemon acid solution, which is added in the first mixed solution, obtains the second mixed solution；The second mixed solution pH is adjusted as 7；
2) by the Co of certain mass3O4It is added in the second mixed solution, is evaporated after being stirred, 1000 degree of oxygen atmosphere
Lower roasting 9h, obtain (1-x) Co3O4·x(Ni0.45Mn0.45Al0.05Sr0.05O2)；
3) according to chemical dosage ratio Ni：Mn：Ti=0.4：1.4：0.2, by the nickel nitrate, manganese acetate and tetrachloro of certain mass
Change titanium to be dissolved in ethanol, form the 3rd mixed solution；Citric acid is dissolved in ethanol, and citric acid solution is added to the 3rd
The 4th mixed solution is obtained in mixed solution；The pH for adjusting the 4th mixed solution is 5.5；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.45Mn0.45Al0.05Sr0.05O2) it is added to the 4th of step 3) the
In mixed solution, it is evaporated after being stirred, 18h is calcined at 400 DEG C of oxygen atmosphere, obtains (1-x-y) Co3O4·x
(Ni0.45Mn0.45Al0.05Sr0.05O2)·y(Ni0.4Mn1.4Ti0.2O4)；
5) product that step 4) obtains is mixed with lithium salts, 3h is calcined at 1050 DEG C of air atmosphere, obtain the positive pole of embodiment 3
Material 0.9LiCoO2·0.01LiNi0.45Mn0.45Al0.05Sr0.05O2·0.09LiNi0.4Mn1.4Ti0.2O4。
Embodiment 4
The present embodiment is 0.91LiCoO2·0.04LiNi0.47Mn0.48La0.05O2·0.05LiNi0.42Mn1.48La0.1O4Altogether
The anode material for lithium-ion batteries of raw structure, the BET of the positive electrode is 0.29m2/ g, D50=20 μm, melt surface is short grained
D50=3μm。
The preparation process of above-mentioned positive electrode is：
1) according to chemical dosage ratio Ni：Mn：La=0.47：0.48：0.05, by the nickel acetate, manganese nitrate, nitre of certain mass
Sour lanthanum is dissolved in the water, and forms the first mixed solution；Tartaric acid is soluble in water, and tartaric acid solution is added to the first mixing
The second mixed solution is obtained in solution；The second mixed solution pH is adjusted as 4.5；
2) by the Co of certain mass3O4It is added in the second mixed solution, is evaporated after being stirred, 1000 degree of oxygen atmosphere
Lower roasting 9h, obtain (1-x) Co3O4·x(Ni0.47Mn0.48La0.05O2)；
3) according to chemical dosage ratio Ni：Mn：La=0.42：1.48：0.1, by the nickel nitrate, manganese acetate and nitre of certain mass
Sour lanthanum is dissolved in the water, and forms the 3rd mixed solution；Citric acid is soluble in water, and citric acid solution is added to the 3rd mixing
The 4th mixed solution is obtained in solution；The pH for adjusting the 4th mixed solution is 5.5；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.47Mn0.48La0.05O2) it is added to the 4th mixing of step 3)
In solution, it is evaporated after being stirred, 2h is calcined at 800 DEG C of oxygen atmosphere, obtains (1-x-y) Co3O4·x
(Ni0.47Mn0.48La0.05O2)·y(Ni0.42Mn1.48La0.1O4)；
5) product that step 4) obtains is mixed with lithium salts, 9h is calcined at 1000 DEG C of air atmosphere, obtain the positive pole of embodiment 4
Material 0.91LiCoO2·0.04LiNi0.47Mn0.48La0.05O2·0.05LiNi0.42Mn1.48La0.1O4。
Embodiment 5
The present embodiment is 0.90LiCoO2·0.03LiNi0.5Mn0.48Ti0.02O2·0.07LiNi0.45Mn1.45Sr0.1O4Altogether
The anode material for lithium-ion batteries of raw structure, the BET of the positive electrode is 0.17m2/ g, D50=25 μm, melt surface is short grained
D50=5μm。
The preparation process of above-mentioned positive electrode is：
1) according to chemical dosage ratio Ni：Mn：Ti=0.5：0.48：0.02, by the nickel nitrate, manganese acetate, tetrachloro of certain mass
Change titanium to be dissolved in isopropanol, form the first mixed solution；Gluconic acid is dissolved in ethanol, and gluconic acid solution is added
The second mixed solution is obtained into the first mixed solution；The second mixed solution pH is adjusted as 6.5；
2) by the Co of certain mass3O4It is added in the second mixed solution, is evaporated after being stirred, under 450 degree of oxygen atmosphere
18h is calcined, obtains (1-x) Co3O4·x(Ni0.5Mn0.48Ti0.02O2)；
3) according to chemical dosage ratio Ni：Mn：Sr=0.45：1.45：0.1, by the nickel acetate, manganese acetate and nitre of certain mass
Sour strontium is dissolved in the water, and forms the 3rd mixed solution；Citric acid is soluble in water, and citric acid solution is added to the 3rd mixing
The 4th mixed solution is obtained in solution；The pH for adjusting the 4th mixed solution is 6；
4) (1-x) Co for obtaining step 2)3O4·x(Ni0.5Mn0.48Ti0.02O2) be added to step 3) the 4th mixing it is molten
In liquid, it is evaporated after being stirred, 10h is calcined at 700 DEG C of air atmosphere, obtains (1-x-y) Co3O4·x
(Ni0.5Mn0.48Ti0.02O2)·y(Ni0.45Mn1.45Sr0.1O4)；
5) product that step 4) obtains is mixed with lithium salts, 15h is calcined at 950 DEG C of air atmosphere, obtain the positive pole of embodiment 5
Material 0.90LiCoO2·0.03LiNi0.5Mn0.48Ti0.02O2·0.07LiNi0.45Mn1.45Sr0.1O4。
Embodiment 6~10
Embodiment 6~10 provide lithium ion battery, respectively including positive plate, negative plate, be interval in positive plate and negative pole
Barrier film between piece, and electrolyte, positive plate include plus plate current-collecting body and the positive electrode active material being distributed on plus plate current-collecting body
Matter layer, positive electrode active material layer include positive electrode, bonding agent and conductive agent；Wherein, embodiment is respectively adopted in embodiment 6~10
1~5 anode material for lithium-ion batteries provided is as positive active material.The charge cutoff voltage of these batteries all for 4.4~
4.7V(vs Li+/Li)。
Comparative example 1
With Li1.02Co0.98Al0.005Mg0.01Ti0.005O2(Mg/Ti doping, Al2O3Cladding) be positive electrode, using with reality
Apply the identical method and structure of example 6~10 and prepare lithium ion battery.
Comparative example 2
With LiCoO2For positive electrode, lithium ion battery is prepared using with the identical method and structure of embodiment 6~10.
The SEM of embodiment 1 and the positive electrode of comparative example 1 difference is as shown in Figure 1 and Figure 2；Infrared spectrum is as shown in Figure 3.Will be real
The positive electrode for applying example 1 and comparative example 1 is uniformly mixed and made into anode sizing agent, and is coated with conductive carbon, Kynoar (PVDF)
Positive pole is formed on plus plate current-collecting body, using lithium piece as negative pole, 2430 button cells are formed in glove box, carry out electrochemistry survey
Examination：Fig. 4 is embodiment 1 and the positive electrode powder of comparative example 1 and the XRD spectra charged under 4.5V；Fig. 5 is embodiment 1 and right
The positive electrode of ratio 1 is in the range of 3.0~4.6V, specific discharge capacity-circulation comparison diagram of 0.5C/0.5C charge and discharge cycles.
It is molten that the anode material for lithium-ion batteries surface of the symbiotic structure of the embodiment of the present invention 1 is can be seen that from Fig. 1 and Fig. 2
Molten bonding structure, melt short grained median particle diameter D50About 1 μm, and can be seen that on the SEM of comparative example 1：The Al of white portion2O3
It is uniformly coated on LiCoO2Surface.
The red of the anode material for lithium-ion batteries of the symbiotic structure of the embodiment of the present invention 1 is can be seen that from Fig. 3 FTIR spectrograms
Outer Absorption Characteristics peak value is 574cm-1, and the characteristic infrared absorption peak value of the positive electrode of comparative example 1 is 571cm-1, characteristic absorption
Spike number is higher, and to represent bond energy stronger, the results showed that：The anode material for lithium-ion batteries of symbiotic structure of the present invention has stronger
Co-O bond energys, thus can effectively suppress cobalt acid lithium structure under high voltage cave in and Co dissolutions.
The cobalt acid lithium that the embodiment of the present invention 1 is can be seen that from Fig. 4 XRD spectra charges under 4.5V and still keeps good
Structural stability, i.e. 003 peak do not divide, and illustrate the anode material for lithium-ion batteries of the symbiotic structure of embodiment 1 and have preferably
Crystal property and structural stability；And the cobalt acid lithium of comparative example 1 is charged under 4.5V and undergone phase transition, i.e., 003 peak has divided, and says
Its bright structural stability is poor.It can be seen that the anode material for lithium-ion batteries of symbiotic structure of the present invention has good knot under high voltages
Structure stability.
From fig. 5, it can be seen that the LiCoO in comparative example 1240 capacity, which are circulated, in 3.0~4.6V is less than 100mAh/g；And
Symbiosis positive electrode circulates 40 capacity still up to 178mAh/g in 3.0~4.6V in the embodiment of the present invention 1.It can be seen that the present invention
The anode material for lithium-ion batteries of the stratiform of preparation-layered-spinel symbiotic structure has good cycle performance under high voltages,
Its reason is：There is the phase transformation by O3 phases to H1-3 phases in cobalt acid lithium, the transition process invertibity is poor near 4.53V, and
The symbiotic structure of positive electrode of the present invention can improve the removal lithium embedded invertibity of cobalt acid lithium under high voltage.
To lithium ion battery progress made from embodiment 6~10, comparative example 1~2, discharge capacity and cycle performance are commented first
Valency, acquired results are shown in Table 1.
Discharge capacity is tested first：At 25 DEG C, with 0.5C constant-current charges to 4.45V, 0.05C constant pressures to 4.45V, stand
5min, 3.0V capacity is then discharged to as discharge capacity first using 0.5C.
Cycle performance is tested：At 45 DEG C, with 0.7C constant-current charges to 4.45V, 0.05C constant pressures to 4.45V, then 1C put
To 3.0V 400 this charge and discharge cycles are repeated, and determine discharge capacity when circulating for the first time and follow for the 400th time in electricity
Discharge capacity during ring, obtain the capability retention after circulation：Capability retention=(electric discharge during the 400th circulation after circulation
Capacity)/(discharge capacity when circulating for the first time) × 100%.
Table 1：Embodiment 6~10 and compare 1~2 lithium ion battery the performance test results
Embodiment 6~10 and the contrast of comparative example 1~2 are can be found that from table 1：Conventional cobalt acid lithium is under 3.0~4.45V
Discharge capacity first be 1785mAh, circulation 400 times after capability retention be only 30%, symbiotic structure positive electrode (1-x-
y)LiCoO2·x(LiNi0.5-aMn0.5-bWa+bO2)·y(LiNi0.5-cMn1.5-dVc+dO4) electric discharge first under 3.0~4.45V
Capacity is more than 1790mAh, and the capability retention after circulating 400 times is more than 80%.It can be seen that relative to conventional LiCoO2, with the present invention
Symbiotic structure anode material for lithium-ion batteries is the lithium ion battery of positive active material, discharge capacity under high voltages and is followed
Ring performance is remarkably improved, because stratiform-layered-spinel symbiotic structure of the present invention has stronger Co-O
It bond energy and structural stability, can effectively suppress the structure collapses of cobalt acid lithium during high voltage cycle, suppress Co dissolutions, improve
The invertibity of removal lithium embedded under high voltage；And the stratiform nickel ion doped in intermediate layer and outermost spinel nickel LiMn2O4 are in high voltage
It is lower to play effective gram volume, the energy density of battery is also improved to a certain extent.
In addition, the contrast by comparative example 1 and comparative example 2 can be seen that：Mg/Ti doping, Al2O3The positive electrode of cladding
Li1.02Co0.98Al0.005Mg0.01Ti0.005O2Although the cycle performance under high voltage can be improved, its electric discharge gram can be significantly reduced and held
Amount, because Al2O3For non-electroactive materials, it is very poor to lead lithium ion, so as to reduce battery to a certain extent
Energy density.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (12)
- A kind of 1. anode material for lithium-ion batteries, it is characterised in that：The positive electrode has stratiform-layered-spinel symbiosis The melting structure of formation, wherein, internal layer is stratiform cobalt acid lithium, and intermediate layer is stratiform nickel ion doped, and outermost layer is spinel nickel manganese Sour lithium；The expression formula of the positive electrode is：(1-x-y)LiCoO2·x(LiNi0.5-aMn0.5-bWa+bO2)·y(LiNi0.5-cMn1.5-dVc+dO4),Wherein, at least one of W Al, Mg, Ti, Sr, La element, at least one of V Al, Mg, Ti, Sr, La element, W, V element may be the same or different, the ＜ ＜ c of a, b≤0.2,0 of 0 ＜ x ＜, 0.1,0 ＜ y ＜ 0.1,0, d≤0.2.
- 2. anode material for lithium-ion batteries according to claim 1, it is characterised in that：The anode material for lithium-ion batteries For melting structure, the short grained median particle diameter D of its melt surface50For 0.01~5 μm.
- 3. anode material for lithium-ion batteries according to claim 1, it is characterised in that：The anode material for lithium-ion batteries For melting structure, the short grained median particle diameter D of its melt surface50For 0.01~2 μm.
- 4. anode material for lithium-ion batteries according to claim 1, it is characterised in that：The anode material for lithium-ion batteries Charge to 4.5V (vs Li+/ Li) under XRD corresponding to 003 peak do not divide.
- 5. anode material for lithium-ion batteries according to claim 1, it is characterised in that：The anode material for lithium-ion batteries BET be 0.1~0.9m2/g。
- A kind of 6. method for preparing the anode material for lithium-ion batteries any one of claim 1 to 5, it is characterised in that Comprise the following steps：1) according to chemical dosage ratio Ni：Mn：W=(0.5-a)：(0.5-b)：(a+b), by soluble nickel salt, manganese salt and other nothings Machine salt is dissolved in the first solvent, forms the first mixed solution；First chelating agent is dissolved in the second solvent, and first is chelated Agent solution, which is added in the first mixed solution, obtains the second mixed solution；The second mixed solution pH is adjusted as 4~8；2) by Co3O4It is added in the second mixed solution, is evaporated after being stirred, is calcined at a certain temperature, obtains by nickel manganese bag The Co covered3O4, i.e. (1-x) Co3O4·x(Ni0.5-aMn0.5-bWa+bO2)；3) according to chemical dosage ratio Ni：Mn：V=(0.5-c)：(1.5-d)：(c+d), by soluble nickel salt, manganese salt and other nothings Machine salt is dissolved in the 3rd solvent, forms the 3rd mixed solution；Second chelating agent is dissolved in the 4th solvent, and second is chelated Agent solution is added in the 3rd mixed solution and obtains the 4th mixed solution；The pH for adjusting the 4th mixed solution is 4~8；4) (1-x) Co for obtaining step 2)3O4·x(Ni0.5-aMn0.5-bWa+bO2) it is added to the 4th mixed solution of step 3) In, it is evaporated after being stirred, is calcined at a certain temperature, obtains (1-x-y) Co3O4·x(Ni0.5-aMn0.5-bWa+bO2)·y (Ni0.5-cMn1.5-dVc+dO4)；5) product for obtaining step 4) is mixed with lithium salts, is calcined, and obtains the lithium ion of stratiform-layered-spinel symbiotic structure Cell positive material.
- 7. the preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：The step 1) with In step 3), soluble nickel salt is nickel acetate and/or nickel nitrate；Soluble manganese salt is manganese acetate and/or manganese nitrate；It is other inorganic Salt is at least one of soluble aluminium salt, magnesium salts, titanium salt, lanthanum salt and strontium salt；First to fourth solvent may be the same or different, It is taken respectively from least one of water, ethanol and isopropanol；The one the second chelating agents may be the same or different, and be taken respectively from lemon At least one of acid, tartaric acid and gluconic acid.
- 8. the preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：The step 2) with In step 4), sintering temperature is 400~1000 DEG C, and roasting time is 1~20h, and calcination atmosphere is air or oxygen.
- 9. the preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：The step 2) with In step 4), sintering temperature is 400~1000 DEG C, and roasting time is 1~20h, and calcination atmosphere is oxygen.
- 10. the preparation method of anode material for lithium-ion batteries according to claim 6, it is characterised in that：The step 5) In, lithium salts Li2CO3, LiOH and LiNO3At least one of, sintering temperature be 800~1050 DEG C, roasting time be 1~ 20h, calcination atmosphere are air or oxygen.
- 11. a kind of lithium ion battery, it includes positive plate, negative plate, the barrier film being placed between positive/negative plate, and electrolysis Liquid, positive plate include plus plate current-collecting body and the positive electrode active material layer being distributed on plus plate current-collecting body, it is characterised in that：It is described just Pole active material layer is using the anode material for lithium-ion batteries of the symbiotic structure any one of claim 1 to 5 as just Pole active material.
- 12. lithium ion battery according to claim 11, it is characterised in that：The lithium ion battery relative to lithium charging Blanking voltage is 4.3V~4.7V.
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| CN105301194B (en) * | 2015-10-30 | 2018-01-16 | 江苏华东锂电技术研究院有限公司 | The detection method of surface of positive electrode active material covered effect |
| CN108565452B (en) * | 2018-01-29 | 2021-04-20 | 哈尔滨工业大学 | Method for treating lithium ion battery anode material by using acidic high polymer |
| CN109755529B (en) * | 2019-01-04 | 2020-09-25 | 散裂中子源科学中心 | Composite oxide Li1-xMn0.8Ni0.2O2And preparation method and application thereof |
| CN109802133B (en) * | 2019-01-16 | 2021-09-21 | 宁德新能源科技有限公司 | Lithium cobaltate precursor, preparation method thereof and lithium cobaltate compound prepared from lithium cobaltate precursor |
| CN111106331B (en) * | 2019-11-12 | 2021-03-09 | 广东邦普循环科技有限公司 | Layered-spinel phase composite positive electrode material and preparation method thereof |
| CN111517375B (en) * | 2020-04-23 | 2022-10-28 | 湖州天丰电源有限公司 | High-voltage high-capacity lithium ion battery positive electrode material and preparation method thereof |
| CN111628147B (en) * | 2020-04-25 | 2022-05-03 | 湖南鑫碳新材料有限公司 | Composite lithium ion battery positive electrode material and preparation method thereof |
| CN112271284B (en) * | 2020-10-28 | 2022-05-17 | 河北省科学院能源研究所 | Modified nickel-rich ternary material and preparation method and application thereof |
| CN112736230B (en) * | 2020-12-30 | 2022-03-18 | 天目湖先进储能技术研究院有限公司 | High-voltage composite spinel-coated cathode material and preparation method thereof |
| CN114094060B (en) * | 2021-10-08 | 2023-05-02 | 中南大学 | Preparation method of high-voltage positive electrode material with core-shell structure |
| CN114566626B (en) * | 2022-03-02 | 2023-08-01 | 北京卫蓝新能源科技有限公司 | Multilayer composite phase structure anode material and preparation method and application thereof |
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